WO1986000625A1

WO1986000625A1 - Polymerization catalyst and manufacturing process thereof

Info

Publication number: WO1986000625A1
Application number: PCT/FR1985/000188
Authority: WO
Inventors: Karel Bujadoux
Original assignee: Societe Chimique Des Charbonnages S.A.
Priority date: 1984-07-05
Filing date: 1985-07-04
Publication date: 1986-01-30
Also published as: AU4604685A; EP0187796B1; FR2567134A1; JPS61502613A; AU579174B2; IN164789B; DE3584961D1; ES8703899A1; ES8609373A1; NO167749B; JPH0784494B2; BR8506812A; IN169069B; ATE70540T1; ES553327A0; PT80772B; NO860812L; EP0187796A1; JP2507286B2; FR2567134B1

Abstract

The polymerization catalyst based on a transition metal compound comprises: A) a mixture of at least one chloride of a transition metal M selected among iron, vanadium and chromium and at least one electrone donor, in respective proportions, such that said chloride is soluble in said donor of electrons, and B) a compound of titanium or vanadium in liquid state, the molar ratio between the metal M and the compound (B) being comprised between 0.3 and 6. Application to the polymerization of ethylene or the copolymerization of ethylene with at least one alpha-olefin under a pressure comprised between 1 and 2.500 bars, at a temperature comprised between 70oC and 320oC.

Description

POLYMERIZATION CATALYST AND MANUFACTURING METHOD THEREOF

The present invention relates to a catalyst for the polymerization of ethylene or for the copolymerization of ethylene and α-olefins as well as a process for the production of said catalyst and a process using said catalyst. It is known from Japanese patent application No. 74 / 46,883 to polymerize ethylene at 90 ° C under 10 bars in the presence of tri-isobutylaluminium and a mixture of the complexes of TiCl ₄ and VCI ₃ with tetrahydrofuran. On the other hand, US Patent No. 4,439,538 describes a catalytic system for the polymerization of olefins comprising: (a) an organometallic compound from groups I to III and (b) a component containing titanium and obtained by the following stages: treatment of an anhydrous ferrous chloride support by at least one electron donor of organic type to form an adduct, grinding of the ferrous chloride and post-treatment of the ferrous chloride adduct ground with a halogenated titanium compound in liquid state. The weight ratio of the electron donor (preferably ethyl benzoate) to ferrous chloride is between 10% and 200% and the treatment is carried out at a temperature of 10 ° to 50 ° C. The weight ratio of the halogenated titanium compound to the grinded ferrous chloride adduct can be between 0.5 and 500. All the examples relate to the polymerization of propylene.

The present invention firstly relates to a catalyst and a catalytic system suitable for the polymerization of ethylene or the copolymerization of ethylene and α-olefins at high temperature and under high pressures. The catalyst according to the invention consists of: (A) a mixture of at least one chloride of a transition metal M chosen from iron, vanadium and chromium and at least one electron donor, in respective proportions such that said chloride is soluble in said electron donor, and (B) a titanium or vanadium compound in the liquid state, the molar ratio of metal M to compound (B) being between 0.3 and 6.

The catalytic system according to the invention comprises, in suspension in at least one saturated or aromatic (cyclo) aliphatic hydrocarbon (preferably having 6 to 12 carbon atoms), (C) at least one organoaluminum compound comprising at least one monochlorodialkylaluminum and is characterized in that it comprises at least one catalyst as described above, the molar ratio of compound (C) to the electron donor being greater than or equal to 1.5.

Compound (A), which is devoid of organoaluminum compound but which comprises a compound of a transition metal M chosen from iron, vanadium and chromium is obtained by contact (i) of at least one electron donor chosen from alcohols preferably having not less than 6 carbon atoms, organocarboxylic acids preferably having not less than 7 atoms carbon, the aldehydes preferably having not less than 7 carbon atoms and the amines, preferably alkylamines having not less than 6 carbon atoms, with (ii) at least one metal chloride M. Per chloride metal M means on the one hand the group of chlorides comprising FeCl ₂ , FeCl ₃ , VCl ₃ and CrCl ₃ and on the other hand compounds containing at least one chlorine atom and having organic groups other than hydrocarbon groups, for example C ₂ -C ₁₀ alkoxy groups such as methoxy, ethoxy, propoxy, butoxy and octoxy groups, C ₆ -C ₂₀ aryloxy groups such as phenoxy, methylphenoxy, 2,6-dimethylphenoxy and naphthoxy groups, acyloxy C groups ₁ -C ₂₀ such as formyloxy groups (HCOO-), a ketoxy (CH ₃ COO-), propionyloxy (C ₂ H ₅ COO-), butyryloxy (C ₃ H ₇ COO-), valeryloxy (C ₄ H ₉ COO-), stearoyloxy (C ₁₇ H ₃₃ COO-) and oleoxyloxy ( C ₁₇ H ₃₁ COO-). Surprisingly, minor amounts of ruthenium chloride RuCl ₃ , for example less than or equal to 1 mol% relative to the metal chloride M, could be added to the latter without departing from the scope of the present invention. Mention may be made, as specific examples of alcohols as electron donor (i), of aliphatic alcohols such as 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol and stearyl alcohol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol and α, α-dimethylbenzyl alcohol; and aliphatic alcohols containing an alkoxy group such as n-butyl cellosolve and 1-butoxy-2-propanol. Alcohols having less than 6 carbon atoms such as methanol, ethanol, propanol, butanol, ethylene glycol and methyl carbitol can also be used as alcohols.

Mention may be made, as examples of organocarboxylic acids suitable as electron donor (i), caprylic acid, 2-ethylhexanoic acid, undecylenic acid, undecanoic acid, nonylic acid and acid octanoic.

Examples of aldehydes suitable as electron donor (i) that may be mentioned include capryl aldehyde, 2-ethylhexyl aldehyde, capraldehyde and dndecyl aldehyde.

Examples of suitable amines as a donor can be cited electrons (i), heptylamine, octylamine, nonylamine, decylamine, lauryl amino, undecylamine and 2-ethylhexylamine.

As examples of compounds (B), mention may be made of tetravalent titanium compounds having the formula Ti (OR) _n X _4-n , where R is a hydrocarbon group, X is a halogen atom, and 0 ≤ n ≤ 4. R represents, for example, a saturated or unsaturated alkyl group of 1 to 20 carbon atoms, which can optionally be substituted by a halogen atom, a lower alkoxy group, etc.

Mention may be made, as specific examples of titanium compounds: TiCI ₄ , TiBr ₄ , Til ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₆ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ . Ti (OC ₃ H ₇ ) 2Cl ₂ . Ti (OC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (OC ₆ H ₅ ) ₃ Cl, Ti (OC ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti (OC ₆ H ₁₃ ) ₄ , Ti (OC ₆ H ₁₁ ) ₄ , Ti (OC ₈ H ₁₇ ) ₄ , Ti (OCH ₂ ( C ₂ H ₅ ) CHC ₄ H ₉ ) ₄ , Ti (OC ₉ H ₁₉ ) ₄ , Tl (OC ₆ H ₃ (CH ₃ ) ₂ ] ₄ , Ti (OCH ₃ ) 2 (OC ₄ H ₉ ) ₂ , Ti (OC ₂ H ₄ Cl) ₄ and Ti (OC ₂ H ₄ OCH ₃ ) _4. Mention may also be made of titanium trichloride (optionally co-crystallized with aluminum trichloride in the form TiCl ₃ , ⅓ AlCl ₃ ) and titanium dichloride after having treated them to make them usable in liquid form. This treatment can be carried out for example by bringing said titanium chloride into contact with the same electron donor (i) as that used for the preparation of the compound ( A), at a temperature between 70 ° and 300 ° C. and for a period greater than or equal to 15 minutes. When this treatment only causes partial dissolution of the titanium chloride, it is preferable able to separate and use only the solubilized part of the titanium compound. As examples of compounds (B), mention may also be made of vanadium compounds having the formula VO (OR) _m X _3-m where R and X are as defined above and 0 ≤ m ≤ 3, or VX ₄ where X is as defined. We can cite as specific examples VOCI ₃ , VO (OC ₂ H ₅ ) Cl, VO (OC ₂ H ₅ ) ₃ , VO (OC ₂ H ₅ ) 1.5Cl ₁ , ₅ VO (OC ₄ H ₉ ) ₃ , VO [OCH ₂ (CH ₂ ) -CHC ₄ H ₉ ] ₃ and VCI ₄ . Typically, the compound (C) comprises at least one monochlorodialkylaluminum of formula AlClRR 'in which R and R', identical or different, represent an alkyl group having from 1 to 12 carbon atoms. Compound (C) can also comprise, in admixture with said monochlorodialkylaluminum, another organoaluminum compound chosen from trialkylaluminiums, tri al kényl aluminums, dialkylaluminum alcoholates, alkylaluminum sesquialcoolates, dichloromonoalkylaluminiums, hydrides of dialkylaluminium, alkylaluminium dihydrides, alkylsiloxalanes and alkylaluminium alkoxychlorides. When the other organoaluminum compound included in compound (C) is a trialkylalu minimum, it is preferably used in a molar ratio, relative to the sum of the transition metals present in (A) and (B), less than or equal to 5. Although less widespread than the corresponding chlorinated compounds, the halogen compounds d organoaluminium in which the halogen is other than chlorine can also enter into the constitution of compound (C). Preferably monochlorodialkylaluminium is the main constituent of compound (C), of which it represents at least half in molar proportion; thus aluminum sesquichlorides fall within the scope of the compounds (C) according to the invention. A second object of the present invention consists of a process for the polymerization of ethylene or the copolymerization of ethylene with at least one α-olefin, under. a pressure between 1 and 2,500 bars, at a temperature between 70º and 320ºC, in the presence of the catalytic system described above. Thus defined, the method according to the invention essentially covers two possibilities of using said catalytic system.

according to a first variant, in which the pressure is chosen between 1 and 50 bars and the temperature is chosen between 70 ° and 200 ° C, the polymerization or copolymerization is carried out in the presence of at least one solvent chosen from aliphatic hydrocarbons, alicyclic, aromatic and their halogen derivatives. Examples of such solvents include pentane, hexane, Theptane, octane, decane, undecane, dodecane, kerosene, cyclohexane, methylcyclopentane, methylcyclohexane, benzene, toluene, xylenes and chlorobenzene. In this variant of the process according to the invention, the duration of the polymerization is generally between 30 minutes and several hours depending on the temperature considered.

- According to a second variant, in which the pressure is chosen between 100 and 2500 bars and the temperature is chosen between 170 ° and 320 ° C, the (co) -polymerization is carried out continuously and in the absence of solvent. A diluent such as butane may, however, be present in a moderate amount, especially when the pressure exceeds 1000 bars. In this variant of the process according to the invention, the residence time of the catalytic system in the (co) polymerization reactor is between 2 and 120 seconds depending on the temperature considered. In both variants, the method according to the invention can be implemented in the presence of hydrogen acting as a transfer agent in order to control the molecular weight of the polymer or copolymer formed. It can also be implemented by injecting into the reactor, if necessary separately from the catalytic system described above, a trialkylaluminium in solution in a saturated hydrocarbon or a mixture of such hydrocarbons. In the case of the high pressure process, the polymerization can be carried out, as desired, in an autoclave reactor comprising one or more reaction zones or else in a tubular reactor. A third object of the present invention consists of a process for manufacturing the catalyst described above, characterized in that:

in a first step, the electron donor and the metal chloride M are reacted at a temperature between 70 ° and 200 ° C and for a period between 2 and 400 minutes to form a soluble compound (A), and

- In a second step, the soluble compound (A) is mixed with the compound (B) at a temperature less than or equal to 120ºC.

Preferably, the manufacture of the catalyst is carried out using, in the first step, the electron donor in an excessive and variable molar quantity depending on the type of electron donor and the type of metal chloride M. The solvent hydrocarbon used in this first step can be chosen from aliphatic, alicyclic, aromatic hydrocarbons and their halogen derivatives.

The following examples are given by way of nonlimiting illustration of the present invention.

EXAMPLE 1

To 3.3 g of ferrous chloride (containing traces of ruthenium chloride RuCl ₃ in an amount of approximately 0.1% by weight) is added under nitrogen atmosphere 38 ml of 2-ethyl hexanol. While stirring, the mixture is gradually heated to the temperature of 150 ° C until a light brown solution of ferrous chloride / 2-ethylhexanol complex (compound A) is obtained.

A 1 liter volume reactor is then successively filled with 600 ml of a C ₁₀ -C ₁₂ cut of dehydrated and purified aliphatic hydrocarbons, of 0.1 millimole of n-butyl titanate and of a fraction (containing 0, 6 millimole of ferrous chloride) from the solution prepared above.

While stirring, this mixture is left to react for 15 minutes at 80 ° C. 10 millimoles of diethylaluminum monochloride are then introduced into the reactor and the reaction is left to react again for 15 minutes at 80 ° C. The polymerization of ethylene is then carried out at a temperature of 80 ° C. and under an absolute pressure of 1.1 bar. The catalytic yield measured is equal to 18,500 grams of polymer per gram of titanium and per hour. EXAMPLE 2

The preparation of the catalytic system of Example 1 is reproduced by replacing, all conditions being equal, the ferrous chloride (containing traces of ruthenium chloride) with vanadium trichloride. The catalytic solution takes on a blackish color after the addition of n-butyl titanate, mauve after the addition of monochlorodiethylaluminum.

The polymerization of ethylene then being carried out under the same conditions as in Example 1, the catalytic yield measured is equal to 1080 grams of polymer per gram of titanium and vanadium and per hour. EXAMPLE 3

The preparation of the catalytic system of Example 1 is reproduced by replacing, all conditions being equal, the ferrous chloride (containing traces of ruthenium chloride) with chromium trichloride.

The polymerization of ethylene then being carried out under the same conditions as in Example 1, the catalytic yield measured is equal to 11,000 grams of polymer per gram of titanium and per hour. EXAMPLE 4 Using the catalytic system prepared in accordance with Example 1, the polymerization of ethylene is carried out at a temperature of 200 ° C. and under a pressure of 7 bars. Under these conditions, a polymer of melt index (measured according to ASTM D 1238-73) is obtained, with a yield of 450 grams per milliatome of titanium, per minute and per mole.1 ^-1 of ethylene. 0.4 dg / min. EXAMPLE 5

Mixing 1 mole of chloride of formula (TiCl ₃ ^_1/3 AlCl ₃₎ for 45 minutes at 150 ° C with 8 moles of 2-ethyl-hexanol so as to obtain a solution (B). On the other hand, 1 mole of VCI ₃ is mixed for 45 minutes at 150 ° C with 9.4 moles of ethyl-2-hexanol so as to obtain a solution (A). In a C ₁₀ -C ₁₂ cut of aliphatic hydrocarbons rendered anhydrous, 25 ml of solution (B) and 33 ml of solution (A) are successively added at 20 ° C. After heating for 2 hours at 80 ° C., a catalyst solution containing 500 millimoles (Ti + V) / liter is obtained. To 44 ml of a C ₁₀ -C ₁₂ cut of hydrocarbons, 10 ml of the catalyst solution are added, then 46 ml of a solution (in the same cut) of monochlorodiethylaluminum at 2 moles / liter. Using the catalytic system thus obtained, the polymerization of ethylene is carried out under the conditions of Example 4 by separately injecting triethylaluminum into the reactor, in a molar ratio equal to 4 relative to the sum Ti + V. 1030 grams of polyethylene are obtained per milliatome of titanium and vanadium, per minute and per mole.l ^-1 of ethylene. EXAMPLE 6

In 652 ml of a C ₁₀ -C ₁₂ cut of dehydrated and purified aliphatic hydrocarbons, 65.2 millimoles of butyl titanate and 95.5 ml of a 0.6 mol / l chloride solution are introduced under nitrogen. of vanadium (containing traces of ruthenium trichloride in an amount of 0.1% by weight) in 2-ethylhexanol. While stirring, it is left to react for 2 hours at 80 ° C, then cooled to 20 ° C. 1.225 mole of monochlorodiethylaluminum are then added slowly, in solution at 1 mole per liter in the same cut of hydrocarbons, then the mixture is left to react for 60 minutes, at 25 ° C.

Using the catalytic system thus prepared, the polymerization of ethylene is carried out at a temperature of 200 ° C. and under a pressure of 7 bars. There is obtained, with a yield of 1080 grams per milliatome of titanium and vanadium, per minute and per mole.l ^-1 , a polymer of melt index (measured according to standard ASTM D 1238-73) equal to 1.1 dg / min.

EXAMPLE 7

The catalytic system prepared in accordance with Example 6 is used to carry out the polymerization of ethylene under the conditions of said example by additionally injecting triethylaluminium into the reactor in an AlEt ₃ / Ti + V molar ratio equal to 4. This gives the polymer with a yield of 1220 grams per milliatome of titanium and vanadium per minute and per mole.l ^-1 of ethylene.

EXAMPLE 8 (comparative) The catalytic system is prepared under the conditions of Example 6 except that the reaction between butyl titanate and vanadium chloride is carried out for 2 hours at 150 ° C.

Under the polymerization conditions of Example 7, the catalytic system thus obtained leads to a yield of 380 grams of polyethylene per milliatom of titanium and vanadium, per minute and per mole.l ^-1 of ethylene.

EXAMPLES 9 and 10

The conditions for preparing the catalytic system of Example 6 (molar ratio V / Ti = 0.9) were reproduced by varying the molar ratio V / Ti. Under the polymerization conditions of Example 7, the polymer was obtained with the following yields R, expressed in grams per milliatome of titanium and vanadium, per minute and per mole.l ^-1 of ethylene. example 9 = V / Ti = 6 R = 1080 example 10 = V / Ti = 0.5 R = 1070 EXAMPLE 11

Using the catalytic system prepared in Example 6, the autoclave reactor with a volume of 0.9 liters is carried out under a pressure of 800 bars and at a temperature of 240 ° C., the copolymerization in continuous mode of a flow comprising 65% by weight of ethylene and 35% by weight of butene-1, in the presence of 0.1% by volume of hydrogen as a transfer agent. Is obtained with a catalytic yield of 6.3 kg per milliatome of titanium and. vanadium, a copolymer with a density of 0.935 g / cm ³ and a melt index (measured according to standard ASTM D 1238-73) equal to 2.6 dg / min. EXAMPLE 12

The catalytic system prepared in Example 6 is used to effect, under the conditions of Example 11 and by further injecting into the reactor of triethylaluminum at an AlEt ₃ / Ti + V molar ratio equal to 2, the copolymerization of l ethylene and butene-1. Obtained, with a catalytic yield of 8.5 kg per milliatome of titanium and vanadium, a copolymer of melt index (measured according to standard ASTM D 1238-73) equal to 1.2 dg / min.

EXAMPLE 13

The catalytic system prepared in Example 6 is used to copolymerize under continuous conditions under the conditions of Example 11 (with the following exceptions: temperature 260ºC; proportion of hydrogen 0.03% by volume) a flow comprising 50% in weight of ethylene and 50% by weight of butene-1. Is obtained with a catalytic yield of 3.2 kg per milliatome of titanium and vanadium, a copolymer of melt index (measured according to standard ASTM D 1238-73) equal to 1.6 dg / min.

Claims

CLAIMS 1. Polymerization catalyst based on transition metal compound, characterized in that it comprises

(A) a mixture of at least one chloride of a transition metal M chosen from iron, vanadium and chromium and at least one electron donor, in respective proportions such that said chloride is soluble in said electron donor, and

(B) a titanium or vanadium compound in the liquid state, the molar ratio of the metal M to the compound (B) being between 0.3 and 6.

2. Catalyst according to claim 1, characterized in that the electron donor is chosen from alcohols having not less than 6 carbon atoms, organocarboxylic acids having not less than 7 carbon atoms, aldehydes n 'having not less than 7 carbon atoms and amines having not less than 6 carbon atoms.

3. Catalyst according to one of claims 1 and 2, characterized in that the compound (B) is a tetravalent titanium compound having the formula Ti (OR) _n X _4-n , where R is a hydrocarbon group, X is an atom halogen, and 0≤ n≤ 4.

4. Catalyst according to one of claims 1 and 2, characterized in that the compound (8) is a treated titanium trichloride or dichloride, to make it usable in liquid form, by bringing said titanium chloride into contact with the same donor d electrons as that used for the preparation of compound (A), has a temperature between 70 ° and 300 ° C and for a period greater than or equal to 15 minutes.

5. Catalyst according to one of claims 1 and 2, characterized in that the compound (B) is a vanadium compound of formula VX4 or VO (OR) _m X ₃ -m, where R is a hydrocarbon group, X is an atom halogen and 0 ≤ m ≤ 3.

6. A method of manufacturing a catalyst according to one of claims 1 to 5, characterized in that αue

in a first step, the electron donor and the metal chloride M are reacted at a temperature between 70 ° and 200 ° C and for a period between 2 and 400 minutes to form a soluble compound (A), and - in a second step, the soluble compound (A) is mixed with the compound (B) at a temperature less than or equal to 120 ° C.

7. Catalytic polymerization system, suspended in at least one saturated or aromatic aliphatic (cyclo) hydrocarbon, comprising

(C) at least one organoaluminum compound comprising at least one monochloro dialkylaluminum, characterized in that it further comprises at least one catalyst according to one of claims 1 to 5, the molar ratio of compound (C) to the electron donor being greater than or equal to 1.5.

8. Process for the polymerization of ethylene or copolymerization of ethylene with at least one α-olefin, under a pressure between

1 and 2,500 bars, at a temperature between 70 ° and 320ºC, in the presence of a catalytic system, characterized in that said catalytic system conforms to claim 7.

9. The polymerization process according to claim 8, the pressure being chosen between 1 and 50 bar and the temperature being chosen between 70º and 200ºC, characterized in that the polymerization or copolymerization is carried out in the presence of at least one solvent chosen from aliphatic, alicyclic, aromatic hydrocarbons and their halogen derivatives.

10. The polymerization process according to claim 8, the pressure being chosen between 100 and 2500 bars and the temperature being chosen between 170 ° and 320 ° C, characterized in that the residence time of the catalytic system in the (co) reactor polymerization is between 2 and 120 seconds depending on the temperature considered.